Color forming photographic development utilizing amino-nu-hydrocarbon substituted beta-amino-acrylamide couplers



Patented May 9, 1950 UNITED STATES PATENT OFFICE Robert Mitchell Leekley, Chicago, 111., assignor to 'E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application July 11, 1946, Serial No. 682,933

15 Claims.

This invention relates to processes of color photography and to compositions and elements therefor which utilize substituted beta-aminoacrylamides as dye intermediates or color formers. It also relates to certain substituted betaaminoacrylamides as new compounds and to their preparation.

An object of this invention is to provide improvements in the art of color photography. A related object is to provide new color-yielding elements, compositions, and processes. A further object is to provide photographic elements with color-yielding layers which do not have a deleterious effect on silver halide grains. A still further object is to provide a new class of color formers for the color-coupling development of silver halide images. Still other objects will be apparent from the following description of the invention.

It has been discovered that amino-N-substituted beta-aminoacrylamides may advantageously be employed in the color-coupling development of exposed silver halide images. They can be used in colloid layers of photographic elements or in alkaline developer solutions. The types which are fast to diffusion in water-permeable colloid layers can be advantageously used in colloid-silver halide emulsion layers or in coactive color-yielding colloid layers adjacent to colloidsilver halide emulsion layers or they may be dissolved in or dispersed in developer solutions with the aid of hydrotropic or dispersing agents. The mobile types are suitable for use in alkaline developer solutions according to well-knownprinciples. They may be incorporated in the eveloper by any convenient method, such as by stirring in a solution. of the color former in a water miscible organic solvent.

The N-substituted beta-aminoacrylamides can readily be made by reacting a primary or secondary amine with a beta-ketoamide color former, that is, a beta-ketoamide which is capable of reacting with an oxidized primary aromatic amino developing agent to form an azomethine dye. A. large number of such beta-ketoamide compounds are known. Suitable ones are described in United States Patents 2,108,602, 2,283,276, 2,299,641, and 2,319,426. They are reacted with the amine (preferably in excess) in a solvent or diluent for the beta-ketoamide. In the case of the normally gaseous amines or those which have a high vapor pressure they are reacted under pressure in a closed reaction vessel. When primary amines are used, the remaining hydrogen atom on the nitrogen atom of the beta-amino group may be acylated by treatment with an acyl halide or carboxylic acid anhydride.

A class of substituted beta-aminoacrylamides useful in the compositions and processes described above may be prepared from beta-ketoamides of the formula IF -Om-( JA L-Ar A H where is an acyl radical of an aliphatic, aromatic, or heterocyclic acid RCOOH and Ar is an aromatic hydrocarbon nucleus. The products so prepared may be represented by the formula It A 11 RI RII where R is a hydrocarbon radical; R" is hydrogen, an acyl radical, or an aliphatic hydrocarbon radical; R has the same significance as in Formula 1; and Ar is an aromatic hydrocarbon nucleus. Thus, Ar may be a benzene, naphthalene, or diphenyl nucleus, unsubstituted or substituted by various groups common in color formers, e. g., nitro, carboxy, alkyl, aryl, cycloalkyl, alkoxy, halogen, etc.

When acylacetamides of aromatic aminoaldehydes or their lower acetals are used for reaction with the amines thereis produced a new class of compounds which have considerable utility as color formers and also as intermediates for the preparation of high molecular weight color formers. Thus, they may be reacted with hydroxyl polymers, e. g., polyvinyl alcohol, partially hydrolyzed hydrophilic polyvinyl esters, hydrolyzed and partially hydrolyzed hydrophilic ethylene/vinyl acetate interpolymers (described in United States Patent 2,386,347) etc., to form hydroxyl polymer acetal color formers. Thus the acylacetamides of meta-aminobenzaldehyde and its acetals with monoalkanols of 1 to 4 carbon atoms and 1,2- and 1,3-alkanediols of 2 to 4 carbon atoms are suitable reactants. They may be prepared by acylation of an acetal of the aminobenzaldehyde with an acyl acetic acid methyl or ethyl ester, followed, if desired, by hydrolysis to the free aldehyde.

The N-substituted beta-aminoacrylamidobenzaldehyde and their lower acetals have the advantage in the preparation of acetals with hydroxyl polymers that no interaction between the aldehyde group and an active methylene group takes place as may occur in the case of the unsubstituted compounds. In addition, complex reactions which may lead to cross linking of the hydroxyl polymer molecules are avoided.

The invention Will be further illustrated by the following examples. All parts are by weight.

Example I Into a cooled mixture of 25 parts acetoacetanilide in 277 parts of benzene is condensed '75 parts of dimethylamine. The reaction vessel is sealed and the mixture allowed to stand at 25-30 C. under the pressure developed for 18 hours. The reactor is cooled to about C. before opening. An additional 285 parts benzene is added and the excess dimethylamine, water, and about half of the benzene are removed by distillation. The residue is cooled to room temperature and filtere'd to yield 24 parts of white crystalline betadimethylaminocrotonanilide melting at 165- 166.5 C. (Knorr, Ber. 25, 777 reports 160 'C.). The product has the structural formula F rI'iQ CHaNCHs O H A latent silver photographic image is developed by treatment of the emulsion for five minutes with a developing solution by adding a solution of two parts beta-dimethylaminocrotonanilide in 63 parts of 95% alcohol to 1,000 parts of the stock solution prepared from the following ingredients by dissolving in 500 parts of water and diluting to 1,000 parts:

Parts para-Aminodiethylaniline hydrochloride 2 Sodium sulfite (anhydrous) 2 Sodium carbonate (anhydrous) Water to make 1000 After washing with water, bleaching the silver image with 4% potassium ferricyanide solution, and fixing with 25% sodium thiosulfate solution, a sharp, bright-yellow image remained.

Example II Reaction of 25 parts acetoacetanilide with parts of methylamine in 227 parts of benzene under the conditions of Example I, yielded '23 parts of beta-methylaminocrotonanilide melting at 140-l4l C. (Knorr, Ber. 25, 771 reports 144.5 C.) The product has the formula HNCHa O H CHsNCH: O H (IJ After recrystalllzing from benzene this compound 2 p-Aminodiethylaniline hydrochloride 4 melts at l64-165 C. Analysis, calculated for C15H20N203: (3:65.21; H=7.25. Found: 0:65.28, 65.14; I-I=7.25, 7.15.

Five parts of this compound are added to parts of a gelatin emulsion and the mixture is coated on paper, exposed, developed, fixed, bleached, and fixed as described in Example I to give a bright-yellow image free of fog.

Example IV A mixture containing 20 parts of finely divided polyvinyl alcohol (completely hydrolyzed and having a 4% aqueous solution viscosity of 8 to 24 centipoises at 20 C.), 5 parts m-(betadimethylaminocrotonamido)benzaldehyde ethylene glycol acetal (see Example III) and 100 parts glacial acetic acid, is heated at 60 C. for three hours and then cooled. The suspended product is removed by filtering. and is washed by repeated slurrying with methanol. A solution is prepared by stirring together at 50-G0 C. ten parts of this polymer, 40 parts of 95% ethyl alcohol, parts of water, and sufficient sodium hydroxide to bring the pH to about 8. To one-half of this solution is added 31 parts of 3N ammonium bromide and two parts of 0.5N potassium iodide. The mixture is stirred at 40 C. while adding a solution of 29 parts of 3N silver nitrate, 50 parts of water, and 17 par-ts of 28% ammonium hydroxide during one minute. After stirring for a total of one-half hour, 150 parts of 15% sodium sulfate solution is added. The precipitated silver halide/color-former emulsion is washed for one hour in running water, after which the excess water is drained off. The remainder of the original polymer solution is added and the mixture stirred at 65 C. for one-half hour. After cooling to 25 C., the emulsion is coated on barytasized white paper. The resulting paper is exposed to form a latentimage, then developed in a solution of the following composition prepared by dissolving the ingredients in 500 parts of water and diluting to 1,000 parts.

Parts 2 Potassium sulfite (anhydrous) 2 Sodium carbonate (anhydrous) 20 Potassium bromide 1 Water to make 1000 The paper is then washed, bleached in 4% potassium ferricyanide, fixed in 25% sodium thiosulfate, and washed. The resulting yellow image is sharp and free of fog.

Example V Reaction of '75 parts of m-acetoacetamidobenzaldehyde ethylene glycol acetal with 80 parts methylamine in 680 parts of benzene by the method described in Example I yields '70 parts of m- (beta-methylaminocrotonamido) benzaldehyde ethylene glycol acetal melting at 75-'7". C. and having a formula similar to that of Example III but containing 1 methyl group attached to the beta-amino nitrogen atom. Analysis, calculated for CmHmNzOat C=64.12; H=6.87; and N=9.36. Found: 0:65.23, 65.15; H='7.30, 7.31; and N=10.05, 10.19. When added to a developer solution as in Example I, the product gives a. clear yellow image.

Example VI A solution of 26.2 parts of the m(beta-methylaminocrotonamido)benzaldehyde ethylene glycol acetal and 15 parts of pyridine in 138 parts methylene chloride is cooled in an ice bath to 5 C.

and a solution of'14 parts of benzoyl chloride in 35 parts of methylene chloride is added with stirring. After five minutes the mixture is removed from the ice bath and allowed to warm up to room temperature While stirring is continued. The product is precipitated by addition of petroleum ether and recrystallized from acetone to give m-[beta-(N-methyhbenzamido)- crotonamidolbenzaldehyde ethylene glycol acetal melting at 147-148 C. and having the formula n oom om-o=cno-r ion I O-OH2 When incorporated in a gelatin emulsion and processed as in Example III, the product gives a bright yellow image free of fog.

Example VII To a suspension of 30 parts of polyvinyl alcohol (see Example IV) in 75 parts of dioxane, is added 7.5 parts of m-[beta-(N-methylbenzamido)cro-- Example VIII A solution of 31.1 parts of ln-bcnaoylacetamidobenzaldehyde ethylene glycol acetal in 180 parts of benzene is cooled and dimethylamine is passed in until a weight gain of 30 parts is noted. Two layers separate. The reaction vessel is sealed and shaken for 24 hours, then allowed to stand at room temperature for three days, by which time the layers coalesce. It is then cooled and opened and the excess dimethylamine, water, and benzene are removed by distillation, the last part under reduced pressure. The residual oil, 33 parts, is m(beta-dimethylaminocinnamido benza1dehyde ethylene glycol acetal having the following probable structure:

When exposed photographic paper is developed in a color developer containing this color former as in Example I, a clear, bright yellow image having excellent spectral characteristics is obtained.

Example IX To a solution of 10.3 parts of m- (beta -dimethylaminocinnamido)benzaldehyde ethylene glycol acetal, 160 parts of ethanol, 2.25 parts of o-sulio benzaldehyde, 45 parts of water, and three parts of 85% phosphoric acid is added 45 parts of polyvinyl alcohol and the suspension is stirred for one hour at 80 C. The polymer is collected on a filter, washed thoroughly with methanol and acetone, and dried. v

A solution is prepared by stirring ten parts of this polymer with 20 parts of ethanol and 170 parts of water at C. for 15 minutes. The resulting clear solution is used to prepare an emulsion as described in Example IV, which is coated on paper and processed to an exceptionally bright-yellow image.

Procedure A A mixture of 425 parts of ethyl acetoacetate, 1.5 parts of dry pyridine and 525 parts of dry xylene is heated to the boiling point and a mixture of 445 parts of m-aminobenzaldehyde ethylene glycol acetal, three parts of dry pyridine and 525 parts of xylene is added with stirring over a period of three hours. The ethanol formed is allowed to distill as fast as it is produoed. Heating is continued for one hour after addition is complete by which time distillation of ethanol ceases. The reaction mixture is allowed to cool to room temperature and the white crystalline solid is collected on a filter. The cake is slurried in 2600 parts of 5% sodium hydroxide and filtered. The filtrate is saturated with carbon dioxide and the solid is collected On a filter, washed with water, and dried. The yield is 368 parts (58%) of white crystalline solid, melting at -86 0. having the structural formula Analysis: Calculated for C13H15NO4: C=62.7; H=6.0; N=5.6. Found: 0:628; H=6.5; N=5.6.

The acetal can be hydrolyzed by dissolving it in acetone and adding a small amount of 1N phosphoric acid. Upon cooling the macetoacetamidobenzaldehyde crystallizes out and can be recrystallized from acetone and has a melting point of 965 to 975 0.

Analysis: Calculated for Gill-111N031 (3:64. 1; H=5.4; N=6.8. Found: 0:644; H=5.5; N=6.8.

In place of the specific amines described in the above examples, there may be substituted various other primary and secondary amines including propylamine, dipropylamine, butylarnine, dibutylamine, oyclohexylamine, dicyclohexylamine, benzylamine, dibenzylamine, betanaphthylaamine, aniline, p-chloroaniline, piperidine, ethanolamine, and diethanolamine. When a long chain amine, e. g., dodecylamine, is used the dye intermediate is rendered non-diffusin and is usefu1 in the preparation of multilayer color Similarly in place of the specific aoylacetamides as set forth in the above examples there may be substituted other such compounds including N-phenylacetoacetanilide, other aroylacetanilides including benzoylacetanilides, N- methyl benzoylacetanilide and furoylacetanilides as well as the beta-ketoamides disclosed in the patents listed above. When the beta-ketcamides contain two acylacetamide radicals, substituents may be introduced on one or both of the keto groups.

The reaction is carried out under suitable conditions according to the reactivity of both the beta-ketoamides and the amine. When the amine is a low molecular weight aliphatic amine, the reaction is carried out at room temperature under the pressure developed by the amine in a closed vessel. Higher pressures can be developed .by heating. When higher" molecular weight amines. are used, the reaction may be carried out at atmospheric pressure or at ele vated temperatures, if necessary, by refluxing in a solvent. The time of reaction varies depending on the reactants andcan be from 1 to 160 hours.

Various other solvents or diluents may be used, for example, carbon tetrachloride, chloroform, toluene, xylene, or dioxane.

Acylating agents which can be used to acylate the reaction products prepared from primary amines include, in addition to benzoyl chloride utilized in Example V, acetyl chloride, acetic anhydride, benzenesulfonyl chloride, toluenesulfonyl chloride, and ethyl chlorocarbonate. In addition, itis possible to prepare the N-acyl amino derivatives of the color-formers by direct reaction of the color former with the appropriate amide. An example of this type is the reaction of acetamide with acetoacetic ester (Canzoneri and Spica, Gazzetta Chimica Italianna 14, 491).

The color formers may be incorporated into emulsions conventionally by dissolving them in a solvent which does not affect the sensitivity of the emulsion and intimately mixing the same with the water-permeable colloid binder, e. g., a gelatin solution or emulsion. A small amount of an alkali metal base is sometimes advantageous in obtaining a rapid and uniform dispersion of the color former throughout the emulsion. The 1 compounds are, remarkably. free of deleterious effects on the photographic sensitivity and chromatic response characteristics of silver halide emulsions, e. g., silver chloride, silver bromide, and silver. chlorobromide, silver-bromide-iodide, etc. emulsions. They may likewise be used in conjunction with the known sensitizing dyes which render the emulsions sensitive to certain additional wave length regions of light. They may also be used in conjunction with emulsion desensitizers, surface modifiers, and emulsion hardening agents and binding agents other than gelatin, e. g., agar agar, hydrophilic cellulose derivatives, e. g., ethyl cellulose, hydrolyzed cellulose acetate, hydrophilic polymers, e. g., polyamides and hydrolyzed ethylene/vinyl acetate interpolymers of United States Patent No. 2,397,866.

They may be incorporated in developer solutions in various known manners, for example, by dissolving them in an organic solvent miscible with water and adding the solution to the aqueous developer solution. They may, if their solubility is sufiicient, be added directly to the bath. In some cases, the use of dispersing agents, such as alkylated naphthalene sulfonates, higher aliphatic alcohol sulfates, higher alkyl sulfonates, mineral oil sulfonates, Turkey red oil, etc., may be employed.

Other developer solutions with which the novel color formers may be used as described in United States Patent 2,299,641.

An advantage of the invention resides in the fact that it provides a large classof utilizahle color formers. Another advantage is that the color formers may be obtained from available initial materials.

The real advantage appears when complex molecules containing several functional groups are used. An example of this is m-acetoacetamidobenzaldehyde ethyleneglycol acetal. When this product is used to prepare polyvinyl acetals by acetal interchange with polyvinyl alcohol in such solvents as dioxane or acetone, side reactions often occur which lead to partial insolubilization of the polyvinyl alcohol. These side reactions are prevented by protection of the active methylene group of the acetoacetanilide through conversion to the substituted beta-aminoacrylamidobenzaldehyde. These compounds can then be used to make soluble polyvinyl acetal color formers. The substituted betaaminoacrylamido derivatives of acylacetamides of m-aminobenzaldehyde acetals are new compounds.

As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

What is claimed is:

1. A photographic developer composition comprising a primary aromatic amino developing agent and an aminonitrogen-hydrocarbon-substituted beta-aminoacrylamide.

2. A photographic developer solution containing a primary aromatic amino developing agent and an aminonitrogen-hydrocarbon-substituted beta-aminoacrylamide.

3. A photographic developer solution containing a primary aromatic amino developing agent, an alkali, and an aminonitrogen-mono-arylsubstituted beta-aminocrotonamide.

i. A photographic developer solution containing a primary aromatic amino developing agent and a compound of the formula wherein R is a hydrocarbon radical, R" is a member taken from the group consisting of hydrogen, acyl, and hydrocarbon radicals, and Ar is an aromatic hydrocarbon nucleus.

5. A photographic element comprising a support bearing light-sensitive silver halides and at least one water-permeable colloid layer containing an aminonitrogen-hydrocarbon-substituted beta-aminoacrylamide.

6. A photographic element comprising a support bearing light-sensitive silver halides and at least one water-permeable colloid layer containing an N-mono-hydrocarbon substituted betaaminoacrylamide.

7. A photographic element comprising a support bearing light-sensitive silver halides and at least one water-permeable colloid layer containing a compound of the formula wherein R is a hydrocarbon radical, R" is a member taken from the group consisting of hydrogen, acyl, and hydrocarbon radicals, and Ar is an aromatic hydrocarbon nucleus.

8. The process which comprises developing a photographic element containing an exposed silver halide layer with a primary aromatic amino developing agent in the presence'of an aminonitrogen-hydrocarbon-substituted beta aminoacrylamide.

9. A photographic developer solution containing a primary aromatic amino developing agent and a compound of the formula wherein R is a hydrocarbon radical, R" is a member taken from the group consisting of hydrogen, acyl, and hydrocarbon radicals, and Ar is an aromatic hydrocarbon nucleus.

10. A photographic element comprising a support bearing light-sensitive silver halides and at least one water-permeable colloid layer containing a compound of the formula AlkylC=CH-CNAr RN-R t 1 1 wherein R is a hydrocarbon radical, R" is a member taken from the group consisting of hydrogen, acyl, and hydrocarbon radicals, and Ar is an aromatic hydrocarbon nucleus.

11. The process which comprises developing a photographic element having an exposed silver halide layer with a developer solution containing a primary aromatic amino developing agent and an alkali in the presence of a beta-methylaminocrotonanilide.

12. The process which comprises developing a photographic element having an exposed silver halide layer with a developer solution containing a primary aromatic amino developing agent and an alkali in the presence of a beta-dimethylaminocrotonanilide.

13. A photographic element comprising a support bearing a colloid silver halide emulsion layer containing a m-(beta-dimethylaminocrotonamido benzaldehyde ethylene glycol acetal.

14. A photographic developer solution containing a primary aromatic amino developing agent and a compound of the formula:

wherein R is a radical taken from the group wherein R is a radical taken from the group consisting of aliphatic and aromatic hydrocarbon radicals, R, is a hydrocarbon radical, R is a member taken from the group consisting of hydrogen, acyl, and hydrocarbon radicals and Ar is an aromatic hydrocarbon nucleus.

ROBERT MITSHELL LEEKLEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,282,001 Russell May 5, 1942 2,307,399 Frohli-ch Jan. 5, 1943 2,319,426 Middleton May 18, 1943 2,325,331 Martin July 27, 1943 2,359,274 Wilson Sept. 26, 1944 2,407,207 Salminen Sept. 3, 1946 2,407,210 Weissberger Sept. 3, 1946 

1. A PHOTOGRAPHIC DEVELOPER COMPOSITION COMPRISING A PRIMARY AROMATIC AMINO DEVELOPING AGENT AND AN AMINONITROGEN-HYDROCARBON-SUBSTITUTED BETA-AMINOACRYLAMIDE. 